Direct production of electrical energy from liquid fuels



E. Jus'rl ET- L I DIRECT PRODUCTION OF ELECTRICAL ENERGY FROM LIQUID FUELS Filed Feb. 9, 1956 -7WIAQIIWI I J/IZ/W/fi/ W f m Feb. 16, 1960- INVENTdRs EDUARDIl/UlqAUGl/STW/NSEL i v 2,925,454- i DIRECT PRODUCTION OF ELECTRICAL ENERGY FROM LIQU D J Eduard Iusti and August Winsel, Braunschweig, Germany,

assignors to R uhrchemie Aktiengesellschaft, Oberhaus'en-Holten, Germany, 'and'Steinkohlen-Elektrizitat Aktiengesellschaft, Essen-Ruhr, Germany, a corporation of Germany Application February 9, 1956, S erial No. 564,607.

20 Claims. (Cl. 136-86) 7 This invention relates to new and useful improvements in: the direct production of electrical energy from liquid fuels.

- Fuel. cells for the direct production ofelectrical energy from fluid fuels are known, These cells. comprise a fuel electrode and an oxygen electrode, which are spaced- ,a-part in an electrolyte bath.v The electrodesare generally in the form of hollow bodies, such as hollow cylin- L drical bodies, and a gaseous oxidizing agent, such as oxygen, air or halogen is passed to the interior-of the oxygen electrode, while a liquidor gaseous fuel is passed to the interior of the fuel'electrode; The oxidizing gas and the fuel are adsorbed and de-adsorbed in the pores of the. oxygen and fuel electrodes, respectively, leaving these electrodes, in the form of ions with the electrode bodies remaining electrically. charged The ions. may then recombine in the electrolyte solution.

In our. copending application, Serial No. 472,( )f84 an ,cdectrode body is described which is particularly adapt- ...alile'for; use as an oxygen electrodein a fueLcelll" This electrode comprises, a shaped porous carbon body, ,as,'

fo amp .a- 9 cy dr al; po o s"; c r n ody;

Patented. Feh- 6 9, 9

- 20 and 90 C, and produce at'these low temperatures a sufiiciently high, current density. Moreover, these electrodes havea high mechanical strength and long opera tional life. In the case of such diffusion electrode, the

gaseous or liquid fuel islnorrnally passed into the porous electrode body from the'inside, while the electrolyte enters from theoutsid'e. The interphase between the fuel and electrolyte phases is in the interior of the porous body and establishes with the electrode surface a three-phase boundary, which alone is electro-chemically active. This three-phase boundary constitutes only a very small fraction of theinner electrode surface, so that, in effect, only a very small fraction of the inner electrode surface is effectifve for the current-producing process.

diagrammatically shows a vertical sectionof anembodiin a high internal resistance R, for the cel1, and a lowcurrent density.

One object of this invention is 'to increase the vGurrent density and decrease the internal resistance of fuel cells of the above-mentioned type, which are operated with liquid fuels. A further object of this invention is a novel fuel cell for the direct production of electrical energy from liquid fuels, which has a low internal resistance and; producesa high current density. These, and still further objects; will become apparent from the following description, read'in conjunction with the drawing which i i ment of afuel cell; in accordance with the finyention.

In accordance with the invention it has been found that it is-not necessary in the operation of-a' fuel ,cellto pass the liquidfuel directly in contact with 'thefuel electrode,

as, forexamplginto the'hollow interior thereof, but that the'fuel' may be completely intermixedywith 'thef elec havingan average porefdiarneter of 'lO-JOQ Angstrom units and an inner surface area .of 10-.50 square meters per gram. The electrode body is produced by rapidly heating a shapedcarbon electrode body toa temperature above about 650 Qandsuddenly cooling'thetb0dY, as, .for example, by quenching,- to temperatures below about 59 C., and repeating the heating and cooling operation at, least one additional time.

In, our co-pending application, Serial No'. 542,434, a 1

double skeleton'catalyst electrode is described, which is I particularly well suited for 1ise;as a fuel electrode in'a fuel cell. 'The electrode comprises a,:carrier skeleton havingmetallic conductivity and 20-80% by weight f Raney. catalyst skeleton granules embedded therein. T116714,

tween about 600 and 1,000" C., and thereafter contact the other inactive component, ,Qf'the Raney alloy, thus forming a Raney catalyst. j

The Raneyalloy is preferably a Raney nickel aluminum alloy, but may be any 'alloy which is composed. of] two or more components, the active component ofrwhich, after dissolving out of the inactive component,- shows a catai lytic effect. Examples of the active component include,

electrode is preferably in the form of a hollow body, such as a hollow cylindrical body,.and is formed by pressing powdered carbon or a lye resistantpowdered metal capable ,ofiforming a sinterablemixture with powdered ,Raney I alloy: together with powdered Raneyalloy under a press a sure'of about 3,000 and,7 ,000,kilogram s per square cen- ,timeter, sintering'the pressedmass at a temperature beingthe sintcred 'mass' with lye to dissolve aluminum or f in addition to nickel, cobalt andiron, while examples of.

the inactive component," i nclude,lin addition .to aluminum, silicon, magnesium, and zinc. The Raney alloys a hamin contemplated have been described for example in; number f m of fuclsswhi'ch. are

in French Patent 729,357. I

'trolyte solution, provided that the' liquid fuel? and the oxyge e o e ar a h o er-l In connection with substantially inert withrespect to water-insoluble fuels the same may be mixed after "the addition "of a dissolving intermediary.

In accordance with the invention, the liquid fuel, as, T

for example, a water-soluble liquidfuel, such as ethyl or methyl alcohol, is no longer separately filled into the hollow s'pace ofthe fuel electrode, but is simplymixed withi theelectrolyte, as,' for example, with a 6-normal solution. Into this liquid mixture, there is immersed on the one hand the fuel electrode, comprising, forexamplefa double skeleton catalystelectrode as described in our co-pending application, Serial No.1 542,434,

and, on the otherhandfth'e 'oxygen'electrode; the material ofwhichmu'st behave indifferently to the dissolved fuel order thatfanelectrochemical oxidation of the fuel "doesnot occurat the oxygen electrode. The re sistanceof an electrode to 'a liquidifuel must be experimentally dete rniin ed iriiea chv case; it i {When directly mixing a water-soluble fuel as, for ex-1 iamplej analcoholfwith'the; electrolyte, 'the admiss'ibl e consent r ationf of the {fuel f is substantiallygiven jbythe' conductivity of the mixture which, for economic reasons, 7

should not be too'lowlf An advantageous value for aloe 1191 is about 5 l 0,%j, ;by weighn'butfthis .v'aluemaybe varied-within the ran e-pf, 2520 by weight; Suitable m ixingaratiosmu'st be experimeiit'ally determined for any given fuel;

Examplesof'water-soluble fuels which may be 'used I are alcoholi'ketones and ethers with not too higha This results iater-soluble liquid fuels, uchas]; 7 methyl or ethyl alcohol, the. same may be directly mixed r withxthe electrolyte solution, while in connection with tionally required.

fatty acid radical bearing 3-20 ethylene oxide groups and an alcohol radical. Water readily adds to the oxygen bridges between the ethylene oxide groups, and this water then constitutes the basis for additions of ions and consequently for an electrical conductivity. The oxygen electrode preferably consists of a shaped porous carbon body having an average pore diameter of 10400 Angstrom units and an inner surface area of 50 square meters per gram, as described in our copending application, Serial No. 472,084.

The fuel electrode used in accordance with the invention no longer need be hollow, as was conventional, but

may, for example, be in the form of a sheet, solid rod,

cylinder, or the like.

The reaction at the highly active fuel electrode proceeds with the electrolyte and the fuel particles, i.e., both ions and molecules being adsorbed side by side at the entire electrode surface. In being adsorbed, the organic fuel molecules are split by the forces of interaction. The split moleculespresent in the chemisorbed state at the catalyst surface react with the electrolyte with the taking up of hydroxyl ions (OH) and give off electrons to the fuel electrode, which is thereby charged negatively. Fresh fuel molecules are continuously sup plied from the liquid phase by diffusion to the electrode adsorbent, which continuously furnishes the reaction products back into the electrolyte space by diffusion with a general tendency toward maximum intermixing or disorder.

Since the electrode, electrolyte and fuel adjoin'at all points of the fuel electrode surface when the fuel and electrolyte are mixed in accordance .with the invention, the entire inner surface area of the fuel electrode is electrochernically active aslcontrasted tofthe single boundary between thethree phases in connection with the prior bodies, having, for example, an average pour diameter of 10-100 -Angstrom' units, and an inner surface area of 10-50 square meters per gram. These electrodes may be'produced by heating a shaped carbon body to temperatures above 650 C. and suddenly chilling the heated bodies'to temperatures below 50 C. with one or several repetitions of the procedure. Conduits are provided for passing an oxidizing gas into the hollow interior of the oxygen electrodes and a current tap or lead is connected .to each oxygen electrode as the positive terminal of'the cell. Positioned on each side of each of the oxygen electrodes are the fuel electrodes 1. These fuel electrodes are in the form of solid discor cylinder-shaped members so constructed as porous, double-skeleton catalyst electrode bodies, having, for example, a nickel Raney, cobalt or iron Raney catalyst granules as an active component. An electrolyte solution fills the container and. is forced to flow therethrough in the direction of tion in the construction of the fuel cell, since fuel electrodes can be in any desired solid form and neednot be in the form of a shaped 'hollow body, as was conven- Due to the use of the entire inner surface of the fuel electrode for. the electro-chemical process, the internal resistance of the cell is decreased. With the addition of the fuel, on the other hand, which is generally a poor electric conductor, the specific resistance of the electrolyte increases, so that a portion of the reduction of the internal resistance is negated. The greater the concentration of the fuel in the electrode, the greater is this effect on the specific resistance of the electrolyte increasing the same. On the other hand, the reactions at the fuel electrode proceed more rapidly as the fuel concentration increases, so that the polarization resistance decreases as V Example The fuel cellas shown in the drawing is in the form of a container or conduit, of, for example, cylindrical.

shape, as defined by the walls 3. The oxygen electrodes 2 extend transversely into the center of the cylindrical container and are in the form of hollow, porous, carbon the arrows by a pump or the like. Alternately, the cylindrical container may be vertically positioned, and the electrolyte maybe allowed to flow throughby gravity flow. The electrolyte flows through the small pores of the double-skelton fuel electrodes 1.

The fuel cell, as shown in the drawing, and having a nickel double-skeleton catalyst fuel electrode, is operated at a temperature of C. by passing oxygen into the interior and through the oxygen electrodes 2, and by pass ing an electrolyte consisting of a 6-normal KOH solution containing ethyl alcohol mixed, therein, slowly through the cylindrical container and through the'porous fuel electrode Lin the direction of flow as indicated by the arrows. The cell was measured in the conventional manner against a saturated calomel electrode. The electromotive force measured at the fuel' electrodetap '4 amounted to 1.04 volts, at 65 C. Since, from'the known tables for'the change of enthalpy in combustion reactions of alcohol, voltages up to 1.09 volts are"calculated, again with respect to calomel and dependent upon the type of finished products, this measured value indicated that in accordance with the invention, a theo- "retical etficienc'y of at least 95% was obtainable for infinitesimal loads. In addition, the construction of the fuel cell was substantially simplified and the reduction in the internal resistance and an increase in the current density was obtained as compared to prior-known fuel cells. 7 At a load of 'milliamperes per square centimeter which greatly exceeded all of the heretofore known current yields obtained with fuel cells by a factor in the 7 order of magnitude of 10-100, the fuel electrode initially polarized with 0.10 volt. With the electrolyte and fuel I admixture remaining stagnant in the cell, the terminal.

voltage of the cellcontinuously dropped as a load was applied for anextended time. At a load of l0 milliamperes per square centimeter, the polarization remain at a stationary level of about 0.09 volt. 1 The drop in the terminal voltage at the high load wa believedcaused by a diffusion of the combustion prod 'ucts into the pores of the electrode obstructing the same. This difficulty could be largely avoided by using either wide-pore electrodes or by efficient agitation of the elec- "trolyte solution. The difficulty could be overcome in the embodiment shown by slowly passing the electrolyte solution through the cell in the direction of flow as indicated by the arrows, as described above. The electrolyte, as the same passes through the small poresof the fuel electrodes 1, continuously provides asupply of fuel and effects the removal of the combustion products from the active surface of the electrode.

With the operation of the fuel cell in a vertical direction, the fresh electrolyte fuel mixture can siowly perculate through the porous electrodes by its owngravity to the bottom of the container, where the liquid with its reaction products may be regenerated and recycled, as, for example, by pumping to the upper portion of the cell.

trode, means for passing an electrolyte solution containing aliquid fuel which is a member of the group conample, fuel oil, diesel oil, liquid'mineral, fuels or the like, the same are mixed in the electrolyte with a dissolving intermediary. Neutral soaps have proven particu- By the addition of about larly good for this purpose. by weight of sucha dissolving intermediary, excellent results may be obtained, with, for example, low-cost fueloils. It couldbe found that it is not only the dissolving intermediary in the fuel cell which is consumed and supplies electrical energy in accordance with the invention. I 1 I Thus, the invention also makes possible the direct electro-chernical utilization ofliquid mineral fuels, which is elfected with high efiiciency.

While the invention has been described in detail with reference to the specific embodiment shown, various changes and modifications will become apparent to. the artisan which fall within the spirit of the invention and the scope of the appended claims.

We claim:

1. A fuel cell for the direct production of electrical energy from a liquid fuel comprising an electrolyte bath containing a liquid fuel which is a member of the group consisting of alcohols, ketones, ethers, paraflins and aromatic hydrocarbons, said group member having not more than 14 carbon atoms in its molecule admixed therein, a porous fuel electrode and a porous oxygen electrode spaced apart in said electrolytebath for the adsorption and deadsorption as ions of fuel 'andoxygen, respectively, leaving the electrodes charged, said liquid fuel and oxygen electrode being substantially inert with respect to each other, and means forpassing an oxidizing gas in contact with said oxygen electrode.

2; Fuelcell according toclalm l, .whichvsaid liquidfuel is a water-soluble fuel dissolved in the electroyte.

- 3. Fuel cell accordingi to claimil, in which saidliq sistingofralcohols, ketones, ethers, paraflins, and aromatic hydrocarbons, said group member having not more than 14 carbon atoms in its molecule dissolved therein :into and through the container and through the pores'of the fuel electrode.

12. A fuel cell according to claim 11, in which said oxygen electrode is in the form of a porous-shaped carbon body'having an inner surface area of 10-50 square meters per gram, and an average pour diameter of10- 100 'Angstrom units.

13. In the process for the operation of a fuel cell, having a porous fuel electrode and a porous oxygen electrode for the adsorption and de-adsorption as ions of fuel and oxygen, respectively spaced apart in an electrolyte bath in which a fuel is maintained in contact with the fuel electrode and an oxidizing gas is passed in contact with the oxygen electrode, the improvement which comprises continuously elfecting the contact of a liquid fuel which is a member of the group consisting of alcohols, ketones, ethers, paraffins and aromatic hydrocarbons, said group member having not more than 14 carbon atoms in its molecule with the fuel electrode by directly admixing said liquid fuel, substantially inert with respect to the oxygen electrode, with the electroliquid fuel is a substantially water-insoluble liquid fuel and in which said admixing is effected with the addition of a dissolving intermediary.v

nid fuelis a substantially water-insoluble liquid fueldis- 7 solvedin the electrolyte bath with a dissolving interme "diary.

4. Fuel cell according to claim 3, in whichfsaid dis} solving intermediary is a neutral soap present in amount 7 of about 10% by weight. u q I,

5. Fuel cell according-to .claim 1, in which said oxy-" gen electrode is in the form of a hollow-shaped, porous i ftrical' energy from fuels, in which a porous fuel eleccarbon body, having an average pore diameter. of 10-100 electrode is a double-skeleton catalyst electrode.

. 8. Fuel cell accordingto; claim 7, in which said fuel electrode is a nickel 'doublerskeleton..catalyst electrode;

9. Fuel cell according toclaim. 1', includingmeans Angstrom units, and an inner surface area; of 10-50 7. Fuel cell according to claim; 1, in which said fuel "16'. Improvement'according to claim 13, in which the electrolyte containing the liquid fuel admixed therewith is caused to flow, through the. fuel electrode and in con;

tact with the oxygen electrode.

' 17. Improvement according to claim 16, in which said iflow 'of the liquid fuel is, effected ata flow rate proportional to theoperational load of the cell.

y 18.;In theprocess for the direct production of electrodeand a porous oxygen electrode forthe adsorption and de-adsorption 'as ions of fuel and oxygen, respeca tively are maintained spaced apart in an'electrolyte bath,

andin which a fuel is maintained in contact with the fuel electrode and an oxidizing gas passed in contact with the oxygen electrode, the improvement which comprises continuously effecting the contact between the fuel eleoq trode and a liquid fuel by admixing said liquid fuel substantially inert with respect ,to the oxygen electrode and which is a member of the group consisting of alcohols, ketones, ethers, paraflins and aromatic hydrocarfor moving the electrolyte bath 'in'contact with the elecq trodes.

'10. Fuel cell according tojclaim in'which said fuel} electrode is in the form of a substantially solid,'nicl tel double-skeleton"catalyst electrode and including. means i for causing the electrolyte bath to flow'through the pores of the fuel electrode and in contact topass the oxygen electrode. a

' 11. A fuel cell for the direct production of electrical 7 energy from a liquid fuel, comprising a container-for an 7 electrolyte bath, a fuel electrode in the form of a sub V stantially solid porous member of double-skeleton catabons, said groupmember having not more than 14 carbon'atoms in its molecule with the electrolyte solution.

- 19. Improvement according to claim 18, in which said liquid fuel is a substantially water-insoluble liquid fuel vandin whichadmixing is effected with the use of a dis solving intermediary.

- 20. Improvementaccording to claim 19, in which the s electrolyte solution with the admixed liquid fuel is caused lyst clectrodematerialfor the adsorption andde-adsorpj tion of fuel as ions substantially covering the cross-section of said container, a shaped hollow porous oxygen electrode positioned in said container in spaced relation I ship to the fuel electrode forthe adsorption. and de-adsorption as ions of oxygen, means for passing an oxiinto the hollow interior of'said oxygen elec-' to flowthrough the fuel electrode in contact with the oxygen electrode.-

References Cited in the file of this patent UNITED STATES PATENTS 567,959 913,390 Iungner Feb. 23, 1909 2,716,670; 7 Bacon Aug. 30, 1955 r l I FOREIGN PATENTS V r 4,921 Great Britain Oct. 16, umv 521,773 Great .Britain t May 30, .1940

Borchers Sept. 22, 1896 UNITED STATES PATENT OFFICE "CERTIFICATE OF CORRECTION patent No, 2,92s 4s4 February 16 1960 Eduard Justi et a1 I It is hereby certified that error appears in the above numbered pat requiring correction and that the said Letters Patent should read as corrected below.

Column l line 68, for "1563,78? and l 628-,l9l" read 1,563,587 and L628, 190

Signed and sealed this 21st day of April 1964.,

(SEAL) Attest: EDWARD Je BRENNER ERNEST W. SWIDER Attesting Officer i v Commissioner of Patents 

1. A FUEL CELL FOR THE DIRECT PRODUCTION OF ELECTRICAL ENERGY FROM A LIQUID FUEL COMPRISING AN ELECTROLYTE BATH CONTAINING A LIQUID FUEL WHICH IS A MEMBER OF THE GROUP CONSISTING OF ALCOHOLS, KETONES, ETHERS, PARAFFINS AND AROMATIC HYDROCARBONS, SAID GROUP MEMBER HAVING NOT MORE THAN 14 CARBON ATOMS IN ITS MOLECULE ADMIXED THEREIN, A POROUS FUEL ELECTRODE AND A POROUS OXYGEN ELECTRODE SPACED APART IN SAID ELECTROLYTE BATH FOR THE ADSORPTION AND DEADSORPTION AS IONS OF FUEL AND OXYGEN, RESPECTIVELY, LEAVING THE ELECTRODES CHARGED, SAID LIQUID FUEL AND OXYGEN ELECTRODE BEING SUBSTANTIALLY INERT WITH RESPECT TO EACH OTHER, AND MEANS FOR PASSING AN OXIDIZING GAS IN CONTACT WITH SAID OXYGEN ELECTRODE. 